Fabrication of composite articles

ABSTRACT

In the fabrication of composite articles, a binder containing hydroxymethylfurfural is employed.

This is a division of application Ser. No. 318,958 filed Nov. 6, 1981,now U.S. Pat. No. 4,439,568.

This invention relates to novel binder compositions useful in thefabrication of composite articles such as fiber reinforced compositearticles.

Fiber reinforced articles such as glass fiber reinforced furfurylalcohol resin articles are well known as being particularly desirablefor use as vessels, containers and other articles used in systemsrequiring a high degree of chemical resistance, high strength,structural stability and so forth. Various methods have been used in thefabrication of fiber reinforced articles, including, for example, "handlayup" fabrication and "spray-up" fabrication, as well as others. Forexample, U.S. Pat. No. 3,850,727 discloses hand layup techniques andU.S. Pat. No. 3,927,139 discloses spray-up techniques for fabricatingfiber reinforced composite articles. The disclosures of these twopatents are incorporated herein by reference thereto.

In the fabrication of fiber reinforced composite articles, binders, andparticularly furan type binders, that is, binders containing derivativesof furan, are used to bind the reinforcing fibers and to impart strengthto the composite articles. Dilution of the furan binders with furfuralin varying amounts has been found advantageous from the standpoint ofincreasing corrosion resistance. Dilution of binders with fufuralimparts high corrosive resistance characteristics and thus its use hasbeen particularly desirable when the reinforced composite articles areintended to be used under corrosive conditions. However, there has beensome objection to the use of furfural-diluted binder systems because ofthe objectionable odor of furfural and in recent years a desire to avoidhuman exposure to furfural vapors.

It has now been unexpectedly found that hydroxymethylfurfural can beadvantageously used in lieu of furfural in furan binder systems. By"furan binder" is meant a composition prepared from compounds having oneor more furan rings therein. The use of hydroxymethylfurfural in suchbinder systems eliminates the objections associated with use of furfuraland thus this discovery is broadly applicable to binders used in variousapplications. The use of 5-hydroxymethylfurfural in lieu of furfural asa diluent in furan binders results in reinforced composite articleswhich exhibit greater retention of flexural strength over periods oftime than articles produced from furfural-diluted binders in accordancewith the prior art. Representative furan binders which are useful infabricating composite articles include, for example, furfuryl alcoholhomopolymer resins, furfuryl alcohol-formaldehyde resins, furfurylalcohol-furfural-formaldehyde resins, furfuryl alcohol-phenol resins,furfuryl alcohol-urea-formaldehyde resins, furfuryl alcohol-urea-phenolresins and the like. Furan binders for fabricating glass laminates aredescribed in U.S. Pat. Nos. 3,594,345 and 3,681,286, the disclosures ofwhich are incorporated herein. These patents disclose binders comprisingfurfuryl alcohol-formaldehyde resins having a formaldehyde-furfurylalcohol ratio of 0.25:1. Most preferred resin binders for fabricatingglass-reinforced laminates are furfuryl alcohol homopolymers.

In accordance with this invention, 5-hydroxymethylfurfural isincorporated with a furan binder at a level of about 5-25% andpreferably at a level of 5-15% by weight of the binder. Thehydroxymethylfurfural is incorporated with the furan binder afterpre-polymerization of the furan resins to a desired viscosity. Theoptimum viscosity for the binder system depends to large extent on themethod of fabrication of the reinforced composite articles. Thus, inhand layup fabrication the entire process is basically a batch processin which the layers of resin and reinforcement are applied alternately.

In hand layup work, and in pre-preg techniques, relatively highviscosities are desirable, although the hand layup techniques use resinswhich are far less viscous than those resins which are left on thereinforcement in the pre-preg techniques.

In hand layup work, however, it is essential that the initial viscosityof the liquid resin be low enough to provide for the formation of arelatively fine spray of catalyzed resin, to provide ready penetrationand wetting by the liquid throughout the fiberous reinforcement and toprovide minimum tendency of the resin to remain adhering to the rolleror other working tool. When the viscosity is too high, the rollers tendto adhere to the resin in the applied reinforcementmaterial-liquid-resin mass, with result that the highly viscousreinforcement material-liquid-resin mass can be disrupted or literallytorn apart as the roller is withdrawn therefrom. In addition todeveloping minimal cohesion between the applied fiber-resin layer andthe resin-wetted working roller, the lower viscosity resins enhance theworking out of air bubbles from the fiber-resin layer.

On the other hand, relatively high viscosities are desirable inasmuch asless shrinkage is encountered upon cure and more manageable or moretolerable exotherms are usually encountered on the shaping element whenhigher viscosity resins are employed. Relatively high initial viscosityis characteristic of liquid resins in which the early stage ofpolymerization has been carried out at least to some extent in asuitable reactor. Naturally, this controlled advancement of theresinification or condensation reaction involves generation anddisposition of whatever exotherm is generated during that particulardegree of advancement. Consequently, the extent of polymerization orcondensation which can be encountered after that resin is catalyzed andapplied to the shaping element is diminished by the degree to which thecontrolled precondensation is carried out in a reactor. Hence, the moreadvanced resins, that is, resins having high viscosity, relativelyspeaking, are also characterized as exhibiting diminished exothermduring the course of cure of the fabricated article.

U.S. Pat. Nos. 3,927,139 and 3,850,727 discuss considerations withrespect to binder viscosity in relation to methods of fabrication.Obtainment of a particular binder viscosity is not a feature of thepresent invention and the binder viscosity will be governed primarily bythe method of fabrication of the composite articles. Pre-polymerizationor pre-resinification of the furan binder using a variety of acidcatalysts can be accomplished by known procedures such as described inU.S. Pat. No. 3,927,139. The binder systems disclosed herein areapplicable in the production of a wide variety of composite articles inwhich a binder is commonly employed. Likewise, various methods offabrication of the composite articles can be utilized as is known in theart and the binder viscosity and its method of application can be variedas is known.

In practice, when the furan binders are used in fabricating compositearticles, the binders are generally cured with the aid of a suitablecatalyst which is usually an acid catalyst. The choice of catalyst isdependent to large extent on the contemplated method of fabrication ofthe composite articles. The method of fabrication governs the desiredcuring time or "bench life" of the catalyzed binder system as discussedin U.S. Pat. No. 3,927,139. Here again, the selection of a particularcatalyst to employ with the hydroxymethylfurfural diluted binder is nota feature of the present invention and a catalyst can be routinelyselected as is known in the art to provide a catalyzed furan bindersystem in accordance with this invention. Merely representative of acidcatalysts for curing furan binders are toluene sulfonic acid, anilinehydrochloric salts, phenol sulfonic acid, acid chlorides, benzenesulfonic acid, sulfonic acid salts, phthaloyl chloride, hydrochloricacid, phosphoric acid, maleic acid, zinc chloride, sulfuric acid and thelike.

The following examples set forth test data which illustrate theadvantages of the present invention.

EXAMPLE 1

In obtaining all of the data set forth in the examples, except ashereinafter specified, reinforced glass laminate articles were made fromfive glass layers, that is, two 10 mil "C" glass chemical resistantsurfacing veils at opposite faces and three chopped strand mat layers inbetween. These reinforced glass laminates were prepared as follows:

Mylar polyester film was supported on a smooth metal surface whichserves as the shaping surface. Approximately 1/6 the total amount ofcatalyzed resin binder was spread on the polyester film. A C-veil wasthen layed on the resin binder and rolled until it was completely wetwith the binder. Then approximately 1/6 of the total amount of catalyzedresin binder was spread over the top of the veil and rolled untiluniform. The first ply of chopped fiberglass filler was layed down androlled until it was completely wet with binder. Approximately 1/3 of thetotal amount of catalyzed resin binder was spread on the laminate and asecond ply of chopped fiberglass was layed down and rolled until all ofthe filler was wet with binder. Then approximately 1/3 of the totalamount of catalyzed binder was spread on the laminate and a third ply offiberglass filler was layed down and rolled until all of the filler waswet with binder. Finally, the final C-veil layer was added and rolleduntil no coated fiberglass protruded from the surface and the laminatewas uniform. The sheets of laminates were allowed to cure overnight andwere subsequently post cured by heating one hour at 140° F., two hoursat 180° F. and one hour at 200° F. The post cure was performed to reducethe overall test time and post curing is not necessary in practice. Theamount of binder used was approximately three times the weight offiberglass utilized.

The reinforcement utilized was a fiberglass available commercially fromPittsburgh Plate Glass Company under the trade designation PPG/ABMcontaining 28% glass fibers by weight.

Binder A comprised a furfuryl alcohol homopolymer diluted with about 19%by weight of furfural and having a viscosity of approximately 600centipoises when measured on a Brookfield viscometer at 25° C. Binder Bcomprised a furfuryl alcohol homopolymer diluted with 20% furfurylalcohol and 10% hydroxymethylfurfural and having a viscosity of about350 centipoises when measured on a Brookfield viscometer at 55° C. As acatalyst for the resin binder A, o-phthaloyl chloride was used in anamount of 3.25 parts per hundred parts of binder. As a catalyst for theresin binder B, o-phthaloyl chloride was used in an amount of 2.5 partsper hundred parts of binder.

The reinforced glass test laminates were evaluated by Cursory CorrosionResistance 18 Media at 150° F. (ASTM C-581 procedure). Throughout thisapplication flexural strength reported as pounds per square inch wasdetermined by the procedure of ASTM D-790 and flexural modulus isreported in pounds per square inch.

Initially, glass laminates prepared using Binder A exhibited flexuralstrength of 20,000 pounds per square inch and a flexural modulus of727,800 pounds per square inch while the glass laminates prepared byusing Binder B exhibited an initial flexural strength of 13,900 poundsper square inch and flexural modulus of 610,000 pounds per square inch.

The results of a 1 year corrosion study are shown in Table I.

                                      TABLE I                                     __________________________________________________________________________    Binder                                                                            Expo.                                                                             Barcol                                                                            R/S                                                                              % Wt. Ch.                                                                           % Swell                                                                            Flex. Str.                                                                         % Ret.                                                                            Flex. Mod.                                                                          % Ret.                                                                            Appearance                       __________________________________________________________________________    MEDIA - 25% Sulfuric Acid TEMP. 150° F.                                A   1 mo.                                                                             53  46 +0.85 +0.38                                                                              16,400                                                                             82  678,100                                                                             93  No Change                            3 mo.                                                                             56  53 +1.32 +0.73                                                                              13,900                                                                             69  650,000                                                                             89  No Change                            6 mo.                                                                             57  55 +1.15 +0.87                                                                              14,200                                                                             71  629,000                                                                             87  No Change                            1 yr.                                                                             58  57 +2.03 +1.35                                                                              14,900                                                                             75  614,000                                                                             84  Sl. Blister                      B   1 mo.                                                                             50  41 +0.26 0    16,800                                                                             121 668,700                                                                             110 No Change                            3 mo.                                                                             54  47 +0.35 -0.28                                                                              15,600                                                                             112 666,100                                                                             107 No Change                            6 mo.                                                                             58  54 +0.60 0.0  12,300                                                                             88  615,100                                                                             101 No Change                            1 yr.                                                                             59  57 +0.65 -0.57                                                                              11,800                                                                             85  579,000                                                                             95  No Change                        MEDIA - 15% Hydrochloric Acid TEMP. - 150° F.                          A   1 mo.                                                                             50  49 +0.47 0     14,200                                                                            71  668,800                                                                             95  No Change                            3 mo.                                                                             55  54 +0.51 0    13,700                                                                             68  590,700                                                                             81  No Change                            6 mo.                                                                             58  55 +0.81 +0.31                                                                              13,700                                                                             68  637,000                                                                             88  No Change                            1 yr.                                                                             60  57 +0.63 -0.62                                                                              14,000                                                                             70  571,000                                                                             78  No Change                        B   1 mo.                                                                             54  46 -0.05 -0.63                                                                              14,600                                                                             105 577,700                                                                             95  No Change                            3 mo.                                                                             56  49 -0.23 -0.42                                                                              13,800                                                                             99  633,300                                                                             104 No Change                            6 mo.                                                                             58  52 +0.04 -0.62                                                                              12,500                                                                             90  562,900                                                                             92  No Change                            1 yr.                                                                             60  53 -0.02 -0.30                                                                              12,500                                                                             90  523,300                                                                             86  No Change                        MEDIA - 5% Nitric Acid TEMP. - 150° F.                                 A   1 mo.                                                                             52  49 -0.49 -0.34                                                                              12,500                                                                             63  583,300                                                                             80  Discoloration                                                                 Exposed Fibers                                                                Both Sides                           3 mo.                                                                             42  43 -4.44 -1.74                                                                              15,700                                                                             78  589,100                                                                             51  Same as 1 month                      6 mo.                                                                             50  47 -5.37 -3.08                                                                              13,723                                                                             69  556,000                                                                             76  Same as 1 month                      1 yr.                                                                             50  47 -3.69 +1.63                                                                              10,100                                                                             50  438,600                                                                             60  Same as 1 month                  B   1 mo.                                                                             54  48 -0.77 -0.84                                                                              18,600                                                                             134 671,700                                                                             110 Same as 1 month                      3 mo.                                                                             49  43 -2.55 -2.07                                                                              12,300                                                                             88  602,500                                                                             99  Same as 1 month                      6 mo.                                                                             49  41 -3.24 -1.81                                                                              15,468                                                                             111 755,000                                                                             124 Same as 1 month                      1 yr.                                                                             50  40 -2.65 -0.63                                                                              10,900                                                                             78  524,300                                                                             86  Same as 1 month                  MEDIA - 25% Acetic Acid TEMP. - 150° F.                                A   1 mo.                                                                             52  47 +1.26 +0.94                                                                              15,300                                                                             77  628,500                                                                             86  No Change                            3 mo.                                                                             50  50 +2.21 +1.17                                                                              13,500                                                                             67  592,400                                                                             51  No Change                            6 mo.                                                                             53  50 +3.17 +3.92                                                                              13,409                                                                             67  535,000                                                                             74  Fiber Bloom                          1 yr.                                                                             52  50 +3.92 +2.65                                                                              11,700                                                                             59  510,600                                                                             70  Fiber Bloom                      B   1 mo.                                                                             50  44 +0.88 0    15,500                                                                             112 634,500                                                                             104 No Change                            3 mo.                                                                             52  48 +1.61 +0.62                                                                              17,900                                                                             129 709,000                                                                             116 5 Tiny Blisters                      6 mo.                                                                             52  48 +2.52 +2.11                                                                              13,400                                                                             96  555,500                                                                             91  Tiny Blisters                        1 yr.                                                                             50  48 +2.92 +2.39                                                                              12,400                                                                             90  496,900                                                                             81  Fine Cracking                    MEDIA - 15% Phosphoric Acid TEMP. - 150° F.                            A   1 mo.                                                                             43  47 +1.49 +1.02                                                                              14,200                                                                             71  621,800                                                                             85  No Change                            3 mo.                                                                             51  49 +2.61 +1.86                                                                              13,500                                                                             67  587,400                                                                             81  No Change                            6 mo.                                                                             52  51 +2.96 +2.52                                                                              10,900                                                                             55  529,800                                                                             73  No Change                            1 yr.                                                                             53  52 +1.89 +1.0 10,700                                                                             54  607,800                                                                             84  Hair Line                                                                     Cracking                         B   1 mo.                                                                             49  45 +1.15 +0.63                                                                              17,700                                                                             127 672,900                                                                             110 No Change                            3 mo.                                                                             48  43 +1.95 +1.25                                                                              16,600                                                                             119 673,000                                                                             110 2 Tiny Blisters                      6 mo.                                                                             56  50 +2.41 +2.99                                                                              13,148                                                                             95  651,000                                                                             100 2 Tiny Blisters                      1 yr.                                                                             58  52 +1.69 +4.60                                                                              12,900                                                                             93  679,800                                                                             111 Sl. Blister                      MEDIA - 5% Sodium Hydroxide TEMP. - 150°  F.                           A   1 mo.                                                                             48  50 +1.31 +0.56                                                                              15,800                                                                             79  594,800                                                                             82  No Change                            3 mo.                                                                             50  48 +3.06 +2.57                                                                              13,600                                                                             68  600,600                                                                             83  Many Sm.                                                                      Blisters                             6 mo.                                                                             52  50 +2.99 +1.87                                                                              11,721                                                                             59  580,000                                                                             80  Many Sm.                                                                      Blisters                             1 yr.                                                                             53  51 +3.00 +6.04                                                                              10,200                                                                             51  540,300                                                                             75  Fiber Bloom                      B   1 mo.                                                                             54  50 +1.12 +0.97                                                                              19,900                                                                             143 747,500                                                                             123 4 Tiny Blist.                                                                 S Side                               3 mo.                                                                             51  46 +1.87 +1.14                                                                              14,300                                                                             103 604,100                                                                             99  2 Tiny Blist.                                                                 S Side                               6 mo.                                                                             50  47 +2.27 +1.10                                                                              12,400                                                                             89  573,000                                                                             88  16 Tiny Blist.                                                                R Side                               1 yr.                                                                             53  50 +2.66 +2.34                                                                              11,000                                                                             79  551,800                                                                             90  Tiny Blisters                    MEDIA - Sat. Sodium Chloride Temp. - 150° F.                           A   1 mo.                                                                             54  52 +0.52 0    14,800                                                                             74  668,300                                                                             92  No Change                            3 mo.                                                                             55  54 +0.47 -0.60                                                                              13,600                                                                             65  640,100                                                                             88  No Change                            6 mo.                                                                             56  57 +0.46 0    14,300                                                                             72  642,200                                                                             88  No Change                            1 yr.                                                                             52  48 +0.06 -3.17                                                                              17,200                                                                             86  684,500                                                                             94  No Change                        B   1 mo.                                                                             50  45 -0.07 -0.90                                                                              15,900                                                                             114 623,000                                                                             102 No Change                            3 mo.                                                                             58  52 -0.40 -0.60                                                                              13,000                                                                             94  587,500                                                                             96  No Change                            6 mo.                                                                             61  53 -0.47 -0.58                                                                              14,380                                                                             103 673,200                                                                             110 No Change                            1 yr.                                                                             57  50 -0.62 +2.84                                                                              15,200                                                                             110 640,400                                                                             105 No Change                        MEDIA - 10% Sodium Carbonate TEMP. - 150° F.                           A   1 mo.                                                                             48  48 +1.55 +0.63                                                                              12,800                                                                             64  611,500                                                                             84  3 Tiny Blisters                      3 mo.                                                                             48  48 +2.50 +1.78                                                                              12,900                                                                             64  570,700                                                                             78  Few Tiny                                                                      Blisters                             6 mo.                                                                             39  48 3.24  +2.65                                                                              12,200                                                                             61  573,600                                                                             79  Few Tiny                                                                      Blisters                             1 yr.                                                                             48  48 +2.36 +3.42                                                                              11,700                                                                             59  558,700                                                                             77  Blistering                       B   1 mo.                                                                             51  43 +1.06 +0.71                                                                              14,900                                                                             107 608,500                                                                             100 No Change                            3 mo.                                                                             50  41 +1.98 +0.94                                                                              17,100                                                                             123 674,100                                                                             111 Few Tiny                                                                      Blisters                             6 mo.                                                                             57  48 +2.51 +0.63                                                                              14,200                                                                             102 739,000                                                                             121 Few Tiny                                                                      Blisters                             1 yr.                                                                             57  48 +2.20 +1.81                                                                              12,200                                                                             88  639,700                                                                             105 Tiny Blisters                    MEDIA - Ethanol TEMP. - 150° F.                                        A   1 mo.                                                                             43  45 +1.62 0    14,100                                                                             71  609,900                                                                             84  No Change                            3 mo.                                                                             42  41 +1.13 +1.75                                                                              16,700                                                                             84  526,100                                                                             72  Numerous Tiny                                                                 Blisters                             6 mo.                                                                             42  42 +3.27 4.31 13,700                                                                             64  464,900                                                                             64  Some Edge                                                                     Cracking                             1 yr.                                                                             38  38 +4.61 +7.64                                                                              12,200                                                                             61  319,700                                                                             44  Numerous Fine                                                                 Cracking                         B   1 mo.                                                                             38  32 -0.88 0    20,400                                                                             147 695,900                                                                             114 No Change                            3 mo.                                                                             40  34 +0.57 +3.09                                                                              15,400                                                                             111 430,200                                                                             70  No Change                            6 mo.                                                                             43  35 +4.08 +6.29                                                                              13,300                                                                             96  437,200                                                                             72  Sl. Fiber Bloom                      1 yr.                                                                             37  34 +4.67 +8.97                                                                              14,600                                                                             105 432,500                                                                             71  Cracking                         MEDIA - 5% Aluminum Potassium Sulfate TEMP. - 150° F.                  A   1 mo.                                                                             46  48 +1.94 +1.37                                                                              17,100                                                                             86  674,700                                                                             93  Tiny Blisters                                                                 S Side                               3 mo.                                                                             48  51 +3.08 +2.60                                                                              14,000                                                                             70  592,100                                                                             81  No Change                            6 mo.                                                                             50  50 3.45  2.99 10,800                                                                             54  516,700                                                                             71  No Change                            1 yr.                                                                             43  47 +3.49 +4.45                                                                              11,000                                                                             55  509,800                                                                             70  Dulling                          B   1 mo.                                                                             48  41 +1.20 +0.88                                                                              14,700                                                                             106 595,900                                                                             98  No Change                            3 mo.                                                                             50  42 +2.73 +1.99                                                                              13,000                                                                             94  607,100                                                                             99  No Change                            6 mo.                                                                             52  40 3.96  4.05 13,300                                                                             96  634,500                                                                             104 Many Small                                                                    Blisters                             1 yr.                                                                             43  35 +4.30 +5.49                                                                              11,600                                                                             84  535,900                                                                             88  Tiny Blisters                    MEDIA - Methyl Ethyl Ketone TEMP. - 150° F.                            A   1 mo.                                                                             32  30 +2.33 +3.39                                                                              12,800                                                                             64  508,500                                                                             70  No Change                            3 mo.                                                                             37  33 +11.48                                                                              +15.00                                                                             12,000                                                                             60  374,600                                                                             51  Sl. Fiber Bloom &                                                             Edge Cracking                        6 mo.                                                                             39  37 9.87  12.89                                                                              10,300                                                                             52  306,200                                                                             42  Sl. Fiber Bloom &                                                             Edge Cracking                        1 yr.                                                                             35  33 +10.62                                                                              +15.03                                                                             12,800                                                                             64  340,700                                                                             47  Fiber Bloom &                                                                 Edge Cracking                    B   1 mo.                                                                             25  14 +5.49 +8.95                                                                              14,000                                                                             101 436,600                                                                             72  Sl. Edge Cracking                    3 mo.                                                                             27  21 +10.55                                                                              +16.68                                                                             12,300                                                                             88  356,000                                                                             58  Same as 1 month                      6 mo.                                                                             40  20 11.83 16.25                                                                              12,200                                                                             88  350,400                                                                             57  Same as 1 month                      1 yr.                                                                             32  29 +10.28                                                                              +20.40                                                                             13,100                                                                             95  353,000                                                                             58  Same as 1 month                  MEDIA - Ethyl Acetate TEMP. - 150° F.                                  A   1 mo.                                                                             36  38 +0.45 +1.92                                                                              13,400                                                                             67  563,500                                                                             77  Sl. Fiber Bloom                      3 mo.                                                                             38  37 +5.64 +5.56                                                                              13,100                                                                             65  363,400                                                                             50  Fiber Bloom,                                                                  Edge Cracking                        6 mo.                                                                             40  37 8.31  10.63                                                                              11,100                                                                             56  322,900   Fiber Bloom                                                                   Edge Cracking                    1 yr.   NO DATA                                                                              --    --   --   --  --    --  NO DATA                          B   1 mo.                                                                             30  12 +1.75 +3.52                                                                              12,200                                                                             88  372,900                                                                             61  No Change                            3 mo.                                                                             31  26 +9.32 +10.86                                                                             12,300                                                                             88  376,800                                                                             62  Sl. Fiber Bloom,                                                              Edge Cracking                        6 mo.                                                                             38  30 10.49 12.85                                                                               9,849                                                                             71  355,000                                                                             58  Sl. Fiber Bloom,                                                              Edge Cracking                        1 yr.                                                                             30  27 +8.08 +16.31                                                                             11,800                                                                             85  344,000                                                                             59  Fiber Bloom                      MEDIA - Monochlorobenzene TEMP. - 150° F.                              A   1 mo.                                                                             40  39 2.21  +0.33                                                                              13,600                                                                             68  567,500                                                                             78  Slight Dulling                       3 mo.                                                                             41  46 +2.29 +3.25                                                                              14,400                                                                             72  467,300                                                                             64  Sl. Fiber Bloom                      6 mo.                                                                             43  48 4.34  4.32 13,417                                                                             67  451,000                                                                             62  Sl. Fiber Bloom                      1 yr.                                                                             38  39 +7.00 +8.91                                                                              13,300                                                                             66  415,900                                                                             57  Sl. Fiber Bloom                  B   1 mo.                                                                             31  24 +3.27 +4.00                                                                              18,100                                                                             130 636,600                                                                             104 No Change                            3 mo.                                                                             38  26 +8.60 +8.57                                                                              12,300                                                                             88  374,400                                                                             61  Sl. Fiber Bloom                      6 mo.                                                                             41  30 13.04 13.98                                                                              --   --  --    --  Sl. Edge Cracking                    1 yr.                                                                             37  34 +15.27                                                                              +13.56                                                                             15,500                                                                             112 481,400                                                                             79  Sl. Edge Cracking                MEDIA - Perchloroethylene TEMP. - 150°  F.                             A   1 mo.                                                                             48  53 -0.17 +0.33                                                                              19,700                                                                             99  775,200                                                                             107 No Change                            3 mo.                                                                             54  54 -1.07 -1.21                                                                              14,800                                                                             74  674,400                                                                             93  No Change                            6 mo.                                                                             57  60 -2.25 -1.52                                                                              14,200                                                                             71  689,000                                                                             94  No Change                            1 yr.                                                                             52  57 -2.00 -0.89                                                                              15,500                                                                             77  749,100                                                                             103 No Change                        B   1 mo.                                                                             50  47 -0.39 -0.32                                                                              15,800                                                                             114 719,000                                                                             118 No Change                            3 mo.                                                                             54  51 -1.90 -2.77                                                                              12,000                                                                             86  639,700                                                                             105 Sl. Pitting on                                                                Edges                                6 mo.                                                                             58  55 -2.73 -1.34                                                                              14,500                                                                             104 688,100                                                                             113 Sl. Pitting on                                                                Edges                                1 yr.                                                                             53  49 -3.08 -1.97                                                                              16,200                                                                             117 762,200                                                                             125 Dulling Rough                                                                 Side                             MEDIA - n-Heptane TEMP. - 150° F.                                      A   1 mo.                                                                             54  52 -0.51 -1.25                                                                              15,900                                                                             80  650,500                                                                              89 No Change                            3 mo.                                                                             58  56 -2.06 -1.85                                                                              13,400                                                                             67  705,900                                                                             97  No Change                            6 mo.                                                                             65  63 -2.72 -2.23                                                                              15,100                                                                             76  724,900                                                                             100 No Change                            1 yr.                                                                             57  56 -3.04 -2.44                                                                              16,900                                                                             97  665,700                                                                             96  No Change                        B   1 mo.                                                                             53  49 -1.11 -1.22                                                                              13,300                                                                             96  668,400                                                                             110 No Change                            3 mo.                                                                             62  54 -3.14 -2.68                                                                              17,200                                                                             124 535,700                                                                             88  No Change                            6 mo.                                                                             65  62 -3.81 -2.42                                                                              18,700                                                                             135 882,500                                                                             145 No Change                            1 yr.                                                                             57  53 -4.41 -1.78                                                                              15,600                                                                             178 815,600                                                                             112 Dulling Rough                                                                 Side                             MEDIA - Kerosene TEMP. - 150° F.                                       A   1 mo.                                                                             51  53 -0.12 -0.30                                                                              14,400                                                                             72  653,100                                                                             90  No Change                            3 mo.                                                                             57  54 -1.22 -1.15                                                                              17,300                                                                             87  719,600                                                                             99  No Change                            6 mo.                                                                             52  59 -1.30 -1.57                                                                              13,200                                                                             66  701,900                                                                             96  No Change                            1 yr.                                                                             55  56 -1.80 -1.65                                                                              11,400                                                                             57  631,000                                                                             87  No Change                        B   1 mo.                                                                             51  47 -0.41 -0.33                                                                              18,500                                                                             133 772,300                                                                             127 No Change                            3 mo.                                                                             54  54 -2.20 -2.11                                                                              14,300                                                                             103 701,900                                                                             115 No Change                            6 mo.                                                                             58  58 -2.23 -1.92                                                                              19,100                                                                             137 801,300                                                                             133 No Change                            1 yr.                                                                             52  49 -3.00 -0.79                                                                              15,500                                                                             112 622,400                                                                             102 Dulling Rough                                                                 Side                             MEDIA - D.I. Water TEMP. - 150° F.                                     A   1 mo.                                                                             46  47 +1.55 +0.93                                                                              14,300                                                                             42  592,900                                                                             81  No Change                            3 mo.                                                                             47  49 +2.90 +2.62                                                                              14,500                                                                             72  597,100                                                                             82  No Change                            6 mo.                                                                             53  50 +3.46 +2.81                                                                              11,628                                                                             58  557,000                                                                             77  No Change                            1 yr.                                                                             48  45 +2.62 +2.38                                                                              11,400                                                                             57  634,000                                                                             87  Sl. Fiber Bloom                  B   1 mo.                                                                             43  41 +1.25 +0.56                                                                              17,300                                                                             124 666,400                                                                             109 No Change                            3 mo.                                                                             48  44 +2.58 +2.38                                                                              14,000                                                                             101 570,300                                                                             93  No Change                            6 mo.                                                                             50  47 +3.84 3.40 11,700                                                                             84  538,300                                                                             88  No Change                            1 yr.                                                                             48  42 +3.76 +4.09                                                                               9,900                                                                             72  449,300                                                                             74  No Change                        MEDIA - Toluene TEMP. - 150° F.                                        A   1 mo.                                                                             47  50 0     -0.32                                                                              12,500                                                                             63  625,800                                                                             86  No Change                            3 mo.                                                                             51  54 -0.74 0    14,700                                                                             74  627,900                                                                             86  Fiber Trailing                       6 mo.                                                                             52  58 -0.76 0    12,624                                                                             63  611,000                                                                             84  Bad Filter                                                                    Trailing                             1 yr.                                                                             45  53 -0.53 +0.60                                                                              15,900                                                                             80  661,500                                                                             91  Severe Fiber                                                                  Trailing                         B   1 mo.                                                                             42  40 -0.33 -0.31                                                                              14,000                                                                             101 653,600                                                                             107 No Change                            3 mo.                                                                             49  44 -1.12 -0.29                                                                              12,900                                                                             93  586,500                                                                             96  No Change                            6 mo.                                                                             50  44 -0.64 +1.39                                                                              16,600                                                                             119 618,600                                                                             101 No Change                            1 yr.                                                                             38  38 +0.77 +4.70                                                                              14,300                                                                             103 615,600                                                                             101 No Change                        __________________________________________________________________________

EXAMPLE 2

Reinforced glass test panels were fabricated as described above using asthe fibrous reinforcement glass fibers as shown in Table II. The panelswere tested by Standard Test Methods ASTM C-581 (for corrosionresistance) and ASTM D-790 (for strength).

Binder A and Binder B were the same as above. A catalyst consisting of 1part of dimethyl phthalate and 7 parts of phthaloyl chloride was usedfor Binder A in an amount of 3.25 parts per hundred parts of binder andfor Binder B in an amount of 2.5 parts per hundred parts of binder.

The results are shown in Table II.

                  TABLE II                                                        ______________________________________                                                         Binder A                                                                             Binder B                                              ______________________________________                                        Flexural Strength   19,185   13,900                                           Flexural Modulus × 10.sup.5                                                                638,000  610,000                                           Glass              1        1                                                 Flexural Strength   22,238   19,176                                           Flexural Modulus × 10.sup.5                                                                680,000  581,000                                           Glass              2        3                                                 Flexural Strength   20,626   22,097                                           Flexural Modulus × 10.sup.5                                                                601,000  712,000                                           Glass              4        5                                                 Flexural Strength   18,164   19,514                                           Flexural Modulus × 10.sup.5                                                                743,000  764,000                                           Glass              6        7                                                 Flexural Strength   19,281   22,516                                           Flexural Modulus × 10.sup.5                                                                742,000  725,000                                           Glass              8        9                                                 ______________________________________                                    

In the above Table II, the glass reinforcement fibers were as follows:

Glass 1 is fiberglass available commercially from Pittsburgh Plate GlassCompany under the trade designation, PPG/ABM containing 28% glass fibersby weight.

Glass 2 is fiberglass available commercially from Owens Corning Companyunder the trade designation, OCF 720 containing 24.6% glass fibers byweight.

Glass 3 is fiberglass available commercially from Owens Corning Companyunder the trade designation, OCF 720 containing 26.5% glass fibers byweight.

Glass 4 is fiberglass available commercially from Owens Corning Companyunder the trade designation, OCF 740 containing 27.5% glass fibers byweight.

Glass 5 is fiberglass available commercially from Owens Corning Companyunder the trade designation, OCF 740 containing 26.3% glass fibers byweight.

Glass 6 is fiberglass available commercially from Certainteed Companyunder the trade designation, CT-M 123 containing 27.3% glass fibers byweight.

Glass 7 is fiberglass available commercially from Certainteed Companyunder the trade designation, CT-M 123 containing 27.7% glass fibers byweight.

Glass 8 is fiberglass available commercially from Certainteed Companyunder the trade designation, CT-M 113 containing 26.9% glass fibers byweight.

Glass 9 is fiberglass available commercially from Certainteed Companyunder the trade desgination, CT-M 113 containing 28.8% glass fibers byweight.

EXAMPLE 3

Following the test procedure described in Example 2, the data set forthin Table III was obtained using different binder systems.

                  TABLE III                                                       ______________________________________                                                     % By Weight                                                      ______________________________________                                        Binder A       100      --      --     --                                     Binder B       --       95      90     75                                     Hydroxymethylfurfural                                                                        --       5       10     --                                     Furfuryl Alcohol                                                                             --       --      --     25                                     Phthaloyl Chloride Catalyst                                                                  3.25     2.5     2.5    2.5                                    Glass Reinforcement*                                                                         1        1       1      1                                      Flexural Strength (psi)                                                                      19,054   17,487  14,972 18,201                                 Flexural Modulus × 10.sup.5                                                            6.93     7.09    6.52   6.14                                   ______________________________________                                         *See Table II                                                            

EXAMPLE 4

Following the test procedures of Example 2, the data set forth in TableIV was obtained with two different glass fiber reinforcement materialsand two binder systems.

                  TABLE IV                                                        ______________________________________                                        Binder A         100      100      --                                         Binder B         --       --       90                                         Hydroxymethylfurfural                                                                          --       --       10                                         Furfuryl Alcohol --       --       --                                         Phthaloyl chloride                                                                             3.25     3.25     2.5                                        Glass Reinforcement*                                                                           1        1        1                                          Flexural Strength                                                                              19,054   23,209   22,232                                     Flexural Modulus × 10.sup.5                                                              6.93     7.31     7.36                                       ______________________________________                                         *See Table II                                                            

EXAMPLE 5

Glass reinforced test panels were prepared as above and tested over athree month period in accordance with the test procedure of ASTM-C-581.The test results are reported in Table V.

                                      TABLE V                                     __________________________________________________________________________            Media at 150° F.                                                       Sulfuric                                                                              Hydrochloric                                                          Acid 25%                                                                              Acid, 15%                                                                             N--Heptane                                                                            Kerosine                                                                              Toluene Water, D.I.                   Binder Systems                                                                        FS  % RT                                                                              FS  % RT                                                                              FS  % RT                                                                              FS  % RT                                                                              FS  % RT                                                                              FS  % RT                      __________________________________________________________________________    A       15,934                                                                             90 15,377                                                                            87  19,421                                                                            110 15,444                                                                            87  12,064                                                                            68  14,140                                                                            80                        Glass 1                                                                       B       21,943                                                                            110 19,265                                                                            97  21,374                                                                            108 21,618                                                                            109 18,827                                                                            95  16,935                                                                            85                        Glass 4                                                                       B        8,572                                                                            105 12,321                                                                            70  18,939                                                                            107 12,635                                                                            71  15,413                                                                            87  14,118                                                                            80                        Glass 7                                                                       __________________________________________________________________________                    Media at 150° F.                                                       Monochloro-                                                                           Ethyl   Methylethyl                                                                           Sodium  Sodium                                        benzene Acetate Ketone  hydroxide                                                                             chloride sat.                         Binder Systems                                                                        FS  % RT                                                                              FS  % RT                                                                              FS  % RT                                                                              FS  % RT                                                                              FS  % RT                      __________________________________________________________________________            A       14,520                                                                            82  13,602                                                                            77  14,977                                                                            85  11,636                                                                            66  16,218                                                                            92                                Glass 1                                                                       B       16,741                                                                            84  21,086                                                                            106 14,725                                                                            74  16,370                                                                            82  20,210                                                                            102                               Glass 4                                                                       B       15,445                                                                            87  16,999                                                                            96  13,330                                                                            75  15,055                                                                            85  16,454                                                                            93                                Glass 7                                                               __________________________________________________________________________     Test Method -- ASTM C581-                                                     Test duration -- 3 Months                                                     FS = Flexural strength by ASTM D790-                                          % RT = % retention of flexural                                                Binder A -- was catalyzed with 3.25 parts per hundred of catalyst             described in Example 2                                                        Binder B -- was catalyzed with 2.5 parts per hundred of catalyst describe     in Example 2                                                             

EXAMPLE 6

Six castings were made of each of the following formulations:

    ______________________________________                                                    Series I Series II                                                                              Series III                                      ______________________________________                                        Binder B      90         90       --                                          Bis-hydroxymethyl-                                                                          --         --       90                                          furfuryl                                                                      Hydroxymethylfurfural                                                                       10         10       10                                          Catalyst (1 part dimethyl                                                                    3          3        2                                          phthalate, 7 parts                                                            phathaloyl chloride)                                                          Carbon flour  --         20       --                                          ______________________________________                                    

The above formulations were cast and post-cured for 1 hour at 140° F., 2hours at 180° F. and 1 hour at 200° F. The strengths which the castingspossessed were determined by making a so-called "biscuit" or briquette,that is, a formation shaped in a characteristic way (a "dog bone" shape)and bonded by the binder being tested. After the so-called biscuit wasformed, it was placed in a machine adapted to determine what the tensileand ultimate yield strengths of the part thus formed were. The shape ofa typical briquette or biscuit is well known to those skilled in the artand accordingly, the characteristics thereof are not discussed furtherherein; for example, however, reference is made to such typical biscuitin a book entitled Steel Foundry Practice, by J. H. Hall, (PentonPublishing Co., Cleveland, Ohio, 1950) where such unit is shown anddescribed on page 8.

The flex tests were conducted in accordance with procedure ASTM D-790and the strength test results are shown below:

                  TABLE VI                                                        ______________________________________                                                     Series I Series II                                                                              Series III                                     ______________________________________                                        Flexural Strength, psi                                                                       5116       6038     2632                                       Flexural Modulus, psi                                                                        450,000    450,000  560,000                                    ______________________________________                                    

In fabricating composite articles, a silane glass or silica or otheradhesion promoter can be used with binders of this invention in anamount ranging from about 0.1% to 3% based on the weight of the binder.Silane adhesion promoters are well known in the art and include forexample, gamma-mercaptopropyltrimethoxysilane,N-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane,beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,gamma-glycidoxypropyltrimethoxysilane,gamma-aminopropyltriphenoxysilane, gamma-aminopropyltribenzoyoxysilane,gamma-aminopropyltrifurfuroxysilane,gamma-aminopropyltri(o-chlorophenoxy)silane,gamma-aminopropyltri(p-chlorophenoxy)silane,gamma-aminopropyltri(tetrahydrofurfuroxy)silane,methyl[2-gamma-triethoxysilypropyl-amino)ethyl amino]3-propionate inmethanol, modified amino-organosilane, Ureido-silane,mercaptoethyltriethoxysilane, chloropropyltrimethoxysilane,vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane,gamma-methacryloxypropyltrimethoxysilane,gamma-methacryloxypropyltri(2-methoxyethoxy)silane,gamma-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane,gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane,N-beta(aminoethyl)-gamma-amino-propyltrimethoxysilane.

Binder compositions in accordance with this invention are particularlyadvantageous for fabrication of fibrous reinforced articles which in useare exposed to corrosive conditions. However, as shown heretofore, thebinders impart excellent strength characteristics and can be usedadvantageously as binders in the manufacture of pressure molded mediumor high density composite articles such as particle board, wafer board,oriented fiber board, matboard, hardboard, pressboard, fiberglass board,etc. and in the manufacture of low density non-molded composite articlessuch as acoustical tile and thermal insulating mats or boards. Variousmethods of manufacturing the pressure molded high density compositearticles and non-molded low density composites are known in the artusing as matrix-forming materials a resinous binder and glass fiber,woody particles such as sawdust, bark, shavings and chips as well asother fibrous lignocellulosic materials such as straw, bagasse, cornstalks, cork and the like. The binder compositions of this invention canbe used in accordance with the known manufacturing procedures.

Those modifications and equivalents which fall within the spirit of theinvention are to be considered a part thereof.

What is claimed is:
 1. In the fabrication of composite articles whereina binder is employed, the improvement which consists in employing as thebinder a resinous furan binder diluted with hydroxymethylfurfural in anamount of about 5 to 25% by weight of the binder composition.
 2. In thefabrication of fiber reinforced composite articles wherein a binder isemployed, the improvement which consists in employing as the binder aresinous furan binder diluted with hydroxymethylfurfural in an amount ofabout 5 to 25% by weight of the binder composition.
 3. In thefabrication of glass fiber reinforced articles wherein a binder isemployed, the improvement which consists in employing as the binder aresinous furan binder diluted with hydroxymethylfurfural in an amount ofabout 5 to 25% by weight of the binder composition.